EP3845616A1 - Lead for pencil for writing, drawing, marking, plotting and/or coloring - Google Patents
Lead for pencil for writing, drawing, marking, plotting and/or coloring Download PDFInfo
- Publication number
- EP3845616A1 EP3845616A1 EP20305003.4A EP20305003A EP3845616A1 EP 3845616 A1 EP3845616 A1 EP 3845616A1 EP 20305003 A EP20305003 A EP 20305003A EP 3845616 A1 EP3845616 A1 EP 3845616A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- advantageously
- pencil
- pencil lead
- lead
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
- B43K19/02—Pencils with graphite; Coloured pencils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
- B43K19/16—Making non-propelling pencils
- B43K19/18—Making pencil writing-cores
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
Definitions
- the present invention relates to a non-calcined, polymer-based pencil lead.
- the main advantage of using a polymer-based pencil lead in a color pencil or graphite pencil is to combine the benefits of a cost-efficient process of co-extrusion where the different layers (lead and casing, and optionally intermediate protective layer), which are polymer-based, can be assembled in one step, with good mechanical performances of the lead.
- the lead is based on a polymer as the matrix, such as ABS (acrylonitrile-butadiene-styrene), PS (polystyrene) or polyolefin.
- ABS acrylonitrile-butadiene-styrene
- PS polystyrene
- polyolefin polyolefin
- leads can be broken inside the wood core, thus being unsatisfactory for consumers.
- associated process is complex and divided into 2 parts: leads preparation (blending, spinning, drying/calcining and/or baking) and wood slats preparation followed by gluing, assembling, pressing and cutting, thus being time and workforce highly consuming. Relevant wood wastes are also generated.
- an objective of the present invention is to obtain a pencil lead having good mechanical properties, such as flexibility and/or shock resistance, and exhibit smoothness and/or softness, and/or glide of the lead and which gives a good laydown, such as quality of the deposit, intensity and/or vividness of the deposit, in particular when used on paper for coloring and/or drawing.
- the inventors have surprisingly found that it is the case when a lamellar mineral filler having a lamellarity index greater than 2.8 is used in the composition of a polymer-based pencil lead.
- Lamellar mineral fillers having such lamellarity index are for example known from US6348536 as functional fillers for thermoplastic material in order to increase the flexural modulus without diminishing the shock resistance.
- a first object of the present invention therefore concerns a polymer-based extrudable non-calcined pencil lead comprising a lamellar mineral filler having a lamellarity index greater than 2.8, advantageously greater than 3.5, in particular greater than 4.
- a second object of the present invention is a pencil comprising a lead according to the invention.
- the lead according to the present invention thus belongs to the category of polymer-based lead, also referred to as synthetic lead, and it is thus non-calcined. Therefore, no calcining/baking step is used in its manufacturing method.
- the term "polymer-based pencil lead” is intended to mean any pencil lead comprising at least one polymer.
- the term “polymer' means compounds (in particular large molecules or macromolecules) comprising many repeated units, in particular at least two repeating units, preferably at least ten repeating units. This polymer thus functions as a matrix for the production of the lead during the manufacturing method. In particular said polymer also governs the mechanical properties, the writing quality and erasing quality in the finished product.
- the total polymer content of the pencil lead according to the invention is in the range 20 - 45%, advantageously 25 - 40 %, more preferably 30-40%, by weight relative to the total weight of the lead.
- the polymer of the lead is selected from the group consisting of homo or copolymers of polyesters; homo or copolymers of polyolefins (PO) such as polyethylene, polypropylene and mixtures thereof; homo or copolymers of styrene polymers, such as polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), styrene-butadiene copolymers (SB), general purpose polystyrene (GPPS), high impact polystyrene (HIPS) and mixtures thereof and mixtures thereof.
- PS polystyrene
- SAN styrene-acrylonitrile copolymers
- ABS acrylonitrile-butadiene-styrene copolymers
- SB styrene-butadiene copolymers
- GPPS general purpose polyst
- the polymer of the lead is selected from the group consisting of homo or copolymers of styrene polymers, advantageously said homo or copolymers of styrene polymers are chosen in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers and mixtures thereof, still more advantageously in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers and mixtures thereof, in particular it is general purpose polystyrene.
- the lead according to the present invention is extrudable, that is to say, that it can be obtained by extrusion.
- it is extruded.
- the lead according to the present invention is advantageously non-expanded.
- advantageously no expansion agent is used in its manufacturing method.
- advantageously the polymer used is not expanded.
- the lead according to the present invention is a pencil lead, that is to say, intended to be used in pencils, in particular in pencils coated with wood or with a synthetic wood material, optionally comprising an intermediate protective layer, in particular as described in patent application WO01/43987 , WO 2016/097554 and WO 2017/220914 .
- the lead according to the present invention comprises at least a lamellar mineral filler having a lamellarity index greater than 2.8, advantageously greater than 3.5, in particular greater than 4.
- the lamellar mineral filler has thus preferably the form of a powder before its addition in the lead according to the invention.
- the lead according to the invention is solid at room temperature.
- the lead according to the present invention is not a powder (i.e. not in the shape of a powder), i.e. the lead is not in a pulverulent form.
- the lead according to the invention is a molded and/or extruded solid composition.
- the flexural strength should be understood as the strength and the shock resistance of the pencil.
- the impact strength can be measured by Charpy impact test according to the standard NF EN ISO 179-1 of 2010.
- the lead according to the invention is characterized in that the pencil flexural resistance is higher than 0.70 daN.
- the term "lamellarity index" characterizes the shape of the particle of the lamellar mineral filler, and more particularly its flatness (large dimension/thickness).
- this lamellarity index will be measured by the difference between, on the one hand, the value of the mean dimension of the particles of the lamellar mineral filler (D L50 ) obtained by a particle size measurement by Malvern laser diffraction using a wet method (standard AFNOR NFX11-666) and on the other hand, the value of the mean diameter (D S50 ) obtained by a measurement by sedimentation using a "Sedigraph" (standard AFNOR X11-683), this difference being related to the mean diameter D S50 .
- Lamellarity index (D L50 - D S50 ) / D S50
- the term "mean diameter D 50" is intended to mean a diameter such that 50% of the particles by weight have a size less than the said diameter.
- the size consists of the equivalent spherical diameter (Stocks diameter). All measurements of the diameters D 50 were either carried out by means of a "Sedigraph” apparatus by gravity sedimentation in accordance with standard AFNOR XI1-683 (D S50 ) or by Malvern laser diffraction using a wet method (standard AFNOR NFX11-666) (D L50 ).
- the mean diameter D S50 of the lamellar mineral filler measured by sedimentation using a "Sedigraph" is between 0.5 and 5 ⁇ m, more particularly between 0.5 and 4 ⁇ m, still more advantageously between 1 and 3 ⁇ m, in particular of between 1.5 and 2.5 ⁇ m.
- the mean diameter D L50 of the lamellar mineral filler measured by Malvern laser diffraction using a wet method is between 2 and 30 ⁇ m, more particularly between 5 and 20 ⁇ m, still more advantageously between 7 and 15 ⁇ m.
- the term "lamellar mineral filler” is intended to mean any mineral filler or any synthetic filler of which the structure consists of a stack of elementary leaves.
- the lamellar mineral filler according to the invention is a colorless or white lamellar mineral filler, mineral or synthetic particles of any shape, more advantageously selected in the group consisting of clay, talc, boron nitride, mica and mixtures thereof, more advantageously in the group consisting of mica, talc and mixtures thereof, still more advantageously it is talc, in particular HAR® talc such as the reference Talc Luzenac Har® T84 sold by Imerys. This talc has in particular the following properties:
- the lamellar mineral filler according to the invention can be obtained by the process as described in US6348536 .
- the lamellar mineral filler is preferably used in pencil lead in order to have an impact on the vividness of the laydown on the paper and/or on the smoothness or softness of the writing/drawing/coloring experience.
- the total lamellar mineral filler content of the pencil lead according to the invention is in the range 5 - 40%, advantageously 10 - 25 %, more advantageously 10 - 15 %, by weight relative to the total weight of the lead.
- a further object of the invention is the use of a lamellar mineral filler having a lamellarity index greater than 2.8 as defined previously to improve the flexural resistance and/or the smoothness, and/or the vividness of a polymer-based extrudable non-calcined pencil lead, in particular when writing/drawing/coloring on paper.
- the pencil lead according to the invention can also contain a slip agent.
- slip agents are able to modify the surface properties of a film and thus lower the friction between film layers and other surfaces.
- the slip agent needs to migrate out of the polymer to the surface and therefore it is advantageous for it to have a degree of incompatibility with the polymer.
- slip agent in the pencil lead composition are: enhance both appearance and function (to improve smoothness and glides), improve the flow characteristic of the polymer during processing. Slip agents are effective because of their natural tendency "to bloom” to the surface of the film after extrusion.
- the slip agent to be used in the pencil lead according to the present invention is advantageously selected in the group consisting of amides such as ethylene bis stearamide, oleamide, erucamide and stearamide, glycerol derivatives such as glycerol esters such as glycerol ethylhexyl polyhydroxystearate, glycerol behenate, glycerol dibehenate, tribehin, glycerol trihydroxystearate and mixtures thereof, esters of stearic acid, in particular tetraester of stearic acid, esters of pentaerythritol such as pentaerythrityl tetrastearate, and mixtures thereof.
- amides such as ethylene bis stearamide, oleamide, erucamide and stearamide
- glycerol derivatives such as glycerol esters such as glycerol ethylhexyl polyhydroxystea
- the slip agent is a glycerol ester, preferably selected in the group consisting of glycerol ethylhexyl polyhydroxystearate, glycerol dibehenate and mixtures thereof.
- the total slip agent content of the pencil lead according to the present invention is in the range 0.5 - 5%, more advantageously 2 - 4 %, by weight relative to the total weight of the lead.
- the pencil lead according to the present invention can advantageously contain at least a coloring agent.
- the coloring agent is selected in the group consisting of dyes, pigments and mixtures thereof, more advantageously in the group consisting of organic or inorganic pigments, dyes or lacquered dyes, coated mica as well as coated or uncoated metal bronzed, TiO 2 , carbon black, graphite and mixture of these coloring agents.
- pigments should be understood as meaning white or coloured, mineral or organic particles of any form, which are insoluble in the medium, and which are intended to color the lead.
- dyes should be understood as meaning white or colored, mineral or organic particles of any form, which are soluble in the medium, and which are intended to color the lead.
- the coloring agent is selected in the group consisting of pigments and mixtures thereof, still more advantageously in the group consisting of organic pigments, TiO 2 and mixtures thereof.
- the pigment is a red, black, yellow, orange, blue, magenta or violet pigment, and mixtures thereof.
- the pigment and/or carbon black can be coated or mixed with a polyolefin wax (for example in the form of a masterbatch, a pigmentary preparation or a dispersion of pigment in a polyolefin wax) as mentioned in WO2016/097555 and WO2016/097533 .
- the coloring agent gives the lead color.
- the total coloring agent content of the pencil lead according to the invention is in the range 2 - 25%, more advantageously 10 - 20 %, by weight relative to the total weight of the lead.
- said pencil is a color pencil lead or a graphite pencil lead, advantageously a color pencil lead.
- the pencil lead according to the present invention contains at least coloring agent (colored pencil lead), the obtained deposit (laydown) when applied on a surface, such as paper, exhibits a good intensity (or vividness) of the color.
- the pencil flexural resistance is higher than 0.70 daN.
- the pencil lead according to the present invention can contain a wax.
- the term "wax” is intended to mean a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, and having a melting point of 30°C or more, which may be up to 180°C
- the melting point corresponds to the transition stage between a fully crystalline or partially crystalline solid state and an amorphous liquid of variable viscosity, as described in ISO 11357-3; 2011.
- the term “transition”, also referred to as “fusion”, is characterized by an endothermic peak in the DSC curve.
- the melting point of wax can be measured by differential scanning calorimetry (DSC) using a TA Instruments Q20 apparatus, on a temperature range from 20 to 90°C, at cooling/ heating speeds of 10°C/minute.
- DSC differential scanning calorimetry
- the waxes may be hydrocarbon-based waxes, lignite-waxes, amide waxes, fatty acids, fatty acid esters, and/or ester waxes, and mixtures thereof, and may be of plant, mineral, animal and/or synthetic origin.
- the waxes have a melting point of greater than 30°C and better still greater than 50°C, which may be up to 180°C.
- the wax according to the invention is selected in the group consisting of ester waxes, chosen among stearates waxes (melting point: 120-160°C) such as calcium stearate, lignite waxes such as montan waxes, amide waxes, hydrocarbon-based waxes such as paraffin (melting point: 50-60°C), fatty acids such as stearic acid and palmitic acid, fatty acid esters and mixtures thereof, preferably ester waxes, more preferably stearate waxes, more advantageously it is calcium stearate. It is indeed particularly advantageous if the wax is formed of calcium stearate or comprises calcium stearate.
- ester waxes chosen among stearates waxes (melting point: 120-160°C) such as calcium stearate, lignite waxes such as montan waxes, amide waxes, hydrocarbon-based waxes such as paraffin (melting point: 50-60°C), fatty acids such as
- the total wax content of the pencil lead according to the invention is in the range 10 - 40%, advantageously 20 - 35 %, by weight relative to the total weight of the lead.
- the pencil lead according to the present invention can contain additional filler, different from the described lamellar mineral filler having a high lamellarity index, such as mineral fillers, for example chosen from phyllosilicates, chalk, barite, kaolin, bentonite and mixtures thereof.
- mineral fillers for example chosen from phyllosilicates, chalk, barite, kaolin, bentonite and mixtures thereof.
- it does not contain any other filler than the lamellar mineral filler having a lamellarity index greater than 2.8 according to the invention.
- the pencil lead according to the present invention can contain an additive.
- This additive can be selected from additives which are well known to the person skilled in the art in the field of pencil leads, advantageously it is selected in the group consisting of lubricants such as zinc stearate, plasticizers such as phthalate, adipate, benzoate, sebacate and/or citrate plasticizers, in particular dibenzoate, surface-active agents, thermal stabilizers and mixtures thereof.
- the total additive content of the pencil lead according to the invention is in the range 3 - 10%, advantageously 5 - 9 %, by weight relative to the total weight of the lead.
- the pencil lead according to the invention can be a color pencil lead or a graphite pencil lead, advantageously it is a color pencil lead.
- the coloring agent comprises graphite, carbon black or mixture thereof.
- the pencil lead has a diameter between 2 and 3.9 mm; advantageously it is a lead having a diameter between 2 and 2.3 mm (thin lead) or a lead having a diameter between 3 and 3.8 mm (thick lead) or a lead having a diameter between 3.4 and 3.8 mm (very thick lead).
- the lead according to the present invention can have a hexagonal, round or triangular cross section, advantageously a round or hexagonal cross section.
- the lead according to the present invention can be manufactured via processes that are well known to those skilled in the art.
- the lead according to the present invention thus has sufficient color vividness while at the same time having good mechanical properties, in particular in terms of flexural strength and/or impact strength, and while producing a continuous deposit on paper with smoothness.
- the flexural strength should be understood as the strength and the shock resistance of the pencil.
- the impact strength can be measured by Charpy impact test according to the standard NF EN ISO 179-1 of 2010.
- the invention also relates to a pencil comprising a lead according to the present invention, in particular a pencil coated with wood or with synthetic wood material, comprising optionally an intermediate protective layer, for example, as described in patent applications WO 01/43987 , WO 2016/097554 and WO 2017/220914 .
- the pencil according to the invention can be a color pencil or a graphite pencil, advantageously it is a color pencil.
- the pencil according to the invention is obtained by coextrusion of the lead and of the synthetic wood material and optionally of the intermediate protective layer.
- the synthetic wood material is based on styrene polymer
- the intermediate protective layer can also plays the role of adhesion layer if the lead comprises a polyolefin polymer and advantageously the intermediate protective layer can comprise a mixture of EVA and of polystyrene as described in WO 2016/097554 or an ethylene (C1-C4 alkyl) acrylate copolymer, alone or as a blend with a styrene polymer as described in WO2017/220914 .
- the synthetic wood material is expanded so as to have a density equivalent to natural wood.
- the pencil according to the invention comprises an additional decorative layer, advantageously of varnish, surrounding the synthetic wood material, in particular concentrically.
- the decorative layer is made of a material that is compatible with that of the synthetic wood material.
- the pencil according to the present invention can have a hexagonal, round or triangular cross section, advantageously a round or hexagonal cross section.
- it can comprise a means for erasing, such as an eraser, at the unsharpened end of the pencil.
- a means for erasing such as an eraser
- the invention finally concerns the use of a lamellar mineral filler having a lamellarity index greater than 2.8 as defined above to improve the flexural resistance and/or the smoothness, and/or the vividness of a polymer-based extrudable non-calcined pencil lead.
- the pencil flexural resistance test was carried out in order to check the strength and the shock resistance of the pencil.
- test protocol is as follows:
- the measurement of colorimetry can be measured.
- the "vividness” should be understood as the intensity of the deposit i.e. laydown of the pencil when applied on a surface.
- the vividness can be measured by colorimetry test by measuring the color difference ⁇ C between a sample color and a comparative color.
- the density of the color of the deposit has been measured in the CIE L*a*b* system using a KONICA MINOLTA CM-3610 A model spectrocolorimeter in the CIE L a b system (illuminant: D65, angle 10°, specular components included).
- L* indicates the lightness of the color of the deposit. The lowest is the value of L, the most intense (or “darker”) is the color of the deposit.
- the chromaticity coordinates are expressed by the parameters a* and b*, a* indicating the axis of red/green shades and b* the axis of yellow/blue shades.
- the leads of examples 1, 2, 3 and 4 according to the invention which comprise a high lamellarity mineral filler have enhanced flexural properties and color vividness compared to the leads of comparative examples 1 and 2 wherein said high lamellarity mineral filler has been replaced by a low lamellarity mineral filler.
- the smoothness, the glide as well as the softness of the lead has been evaluated by writing, drawing and/or coloring manually with the leads according to examples 1 to 4 and it has been observed that they deliver an effortless and smooth-gliding writing, drawing and/or coloring experience on paper.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
- The present invention relates to a non-calcined, polymer-based pencil lead.
- The main advantage of using a polymer-based pencil lead in a color pencil or graphite pencil, is to combine the benefits of a cost-efficient process of co-extrusion where the different layers (lead and casing, and optionally intermediate protective layer), which are polymer-based, can be assembled in one step, with good mechanical performances of the lead. For these purposes, the lead is based on a polymer as the matrix, such as ABS (acrylonitrile-butadiene-styrene), PS (polystyrene) or polyolefin. This polymer part brings resistance, especially shock resistance, to drop test (i.e. when pencil falls on the floor), avoid the formation of cracks on all the pencil long and prevent from split leads. Also these polymers are easily transformed with high outputs by extrusion and enable to get a consistent compound with pigments, fillers and additives dispersed inside. The drawback concerns mostly the writing/coloring experience. Indeed, contact to the paper is modified due to the polymer, being not as smooth with a rich and vivid deposit as a traditional wood case lead (calcined lead) can be. Depending on the polymer, friction coefficient on paper is high, then scratchy or sticky sensations can be perceived by the consumer who needs to apply more pressure to get an acceptable laydown.
- On the contrary, traditional wood case leads (calcined or baked leads) for pencil are not based on polymer binder but on natural fillers, which have been mixed with pigments, additives and a film forming binder such as cellulosic binder, preliminarily dried, the lead being calcined or baked in the process of preparation. Then contact to the paper is not disturbed by any polymer element since it has disappeared during the calcining/baking step, coloring is smooth and glides better on paper. Color is also more vivid. The drawback of this type of lead is the shock resistance, the lead being sensitive to drop test, and breakage at sharpening. Baked/calcined leads have no more resilience to absorb mechanical stress. Then leads can be broken inside the wood core, thus being unsatisfactory for consumers. Moreover, associated process is complex and divided into 2 parts: leads preparation (blending, spinning, drying/calcining and/or baking) and wood slats preparation followed by gluing, assembling, pressing and cutting, thus being time and workforce highly consuming. Relevant wood wastes are also generated.
- Therefore it would be interesting to obtain a pencil lead combining the properties of a polymer-based lead (such as cost-efficient process of co-extrusion, only one step during the process, good mechanical performances) and the properties of a traditional calcined or baked lead (such as smoothness, easiness of the deposit, vivid color laydown, smoothness on the paper). In particular, an objective of the present invention is to obtain a pencil lead having good mechanical properties, such as flexibility and/or shock resistance, and exhibit smoothness and/or softness, and/or glide of the lead and which gives a good laydown, such as quality of the deposit, intensity and/or vividness of the deposit, in particular when used on paper for coloring and/or drawing.
- The inventors have surprisingly found that it is the case when a lamellar mineral filler having a lamellarity index greater than 2.8 is used in the composition of a polymer-based pencil lead.
- Lamellar mineral fillers having such lamellarity index are for example known from
US6348536 as functional fillers for thermoplastic material in order to increase the flexural modulus without diminishing the shock resistance. - However, it was never described nor suggested that such filler could be used in pencil lead in order to have the above mentioned properties, and in particular to have an impact on the vividness of the laydown on the paper, in particular on the vividness of the colored laydown and/or on the smoothness, or softness of the writing/coloring experience.
- A first object of the present invention therefore concerns a polymer-based extrudable non-calcined pencil lead comprising a lamellar mineral filler having a lamellarity index greater than 2.8, advantageously greater than 3.5, in particular greater than 4.
- A second object of the present invention is a pencil comprising a lead according to the invention.
- The lead according to the present invention thus belongs to the category of polymer-based lead, also referred to as synthetic lead, and it is thus non-calcined. Therefore, no calcining/baking step is used in its manufacturing method.
- For the purposes of the present invention, the term "polymer-based pencil lead" is intended to mean any pencil lead comprising at least one polymer. According to the present invention, the term "polymer' means compounds (in particular large molecules or macromolecules) comprising many repeated units, in particular at least two repeating units, preferably at least ten repeating units. This polymer thus functions as a matrix for the production of the lead during the manufacturing method. In particular said polymer also governs the mechanical properties, the writing quality and erasing quality in the finished product.
- In an advantageous embodiment, the total polymer content of the pencil lead according to the invention is in the range 20 - 45%, advantageously 25 - 40 %, more preferably 30-40%, by weight relative to the total weight of the lead.
- In another advantageous embodiment, the polymer of the lead is selected from the group consisting of homo or copolymers of polyesters; homo or copolymers of polyolefins (PO) such as polyethylene, polypropylene and mixtures thereof; homo or copolymers of styrene polymers, such as polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), styrene-butadiene copolymers (SB), general purpose polystyrene (GPPS), high impact polystyrene (HIPS) and mixtures thereof and mixtures thereof.
- Advantageously, the polymer of the lead is selected from the group consisting of homo or copolymers of styrene polymers, advantageously said homo or copolymers of styrene polymers are chosen in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers and mixtures thereof, still more advantageously in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers and mixtures thereof, in particular it is general purpose polystyrene.
- The lead according to the present invention is extrudable, that is to say, that it can be obtained by extrusion. Advantageously, it is extruded. The lead according to the present invention is advantageously non-expanded. In fact, advantageously no expansion agent is used in its manufacturing method. In addition, advantageously the polymer used is not expanded.
- The lead according to the present invention is a pencil lead, that is to say, intended to be used in pencils, in particular in pencils coated with wood or with a synthetic wood material, optionally comprising an intermediate protective layer, in particular as described in patent application
,WO01/43987 WO 2016/097554 andWO 2017/220914 . - The lead according to the present invention comprises at least a lamellar mineral filler having a lamellarity index greater than 2.8, advantageously greater than 3.5, in particular greater than 4.
- The lamellar mineral filler has thus preferably the form of a powder before its addition in the lead according to the invention.
- Preferably, the lead according to the invention is solid at room temperature. Preferably, according to the present invention, the lead according to the present invention is not a powder (i.e. not in the shape of a powder), i.e. the lead is not in a pulverulent form.
- Preferably, the lead according to the invention is a molded and/or extruded solid composition.
- To determine the "hardness" of a lead in accordance with the invention, the measurement of flexural strength can be measured. The flexural strength should be understood as the strength and the shock resistance of the pencil. The impact strength can be measured by Charpy impact test according to the standard NF EN ISO 179-1 of 2010.
- According to one advantageous embodiment of the invention, the lead according to the invention is characterized in that the pencil flexural resistance is higher than 0.70 daN.
- For the purposes of the present invention, the term "lamellarity index" characterizes the shape of the particle of the lamellar mineral filler, and more particularly its flatness (large dimension/thickness). In the present invention, this lamellarity index will be measured by the difference between, on the one hand, the value of the mean dimension of the particles of the lamellar mineral filler (DL50) obtained by a particle size measurement by Malvern laser diffraction using a wet method (standard AFNOR NFX11-666) and on the other hand, the value of the mean diameter (DS50) obtained by a measurement by sedimentation using a "Sedigraph" (standard AFNOR X11-683), this difference being related to the mean diameter DS50.
Lamellarity index: (DL50 - DS50) / DS50 - Reference may be made to the article G.BAUDET and J. P. RONA, Ind. Min. Mines et Carr. Les techn. June, July 1990, pp 55-61 which shows that this index is correlated to the mean ratio of the largest dimension of the particle to its smallest dimension.
- For the purposes of the present invention, the term "mean diameter D50" is intended to mean a diameter such that 50% of the particles by weight have a size less than the said diameter. For non-spherical particles, the size consists of the equivalent spherical diameter (Stocks diameter). All measurements of the diameters D50 were either carried out by means of a "Sedigraph" apparatus by gravity sedimentation in accordance with standard AFNOR XI1-683 (DS50) or by Malvern laser diffraction using a wet method (standard AFNOR NFX11-666) (DL50).
- In an advantageous embodiment, the mean diameter DS50 of the lamellar mineral filler measured by sedimentation using a "Sedigraph" (standard AFNOR X11-683) is between 0.5 and 5 µm, more particularly between 0.5 and 4 µm, still more advantageously between 1 and 3 µm, in particular of between 1.5 and 2.5 µm.
- In another advantageous embodiment, the mean diameter DL50 of the lamellar mineral filler measured by Malvern laser diffraction using a wet method (standard AFNOR NFX11-666) is between 2 and 30 µm, more particularly between 5 and 20 µm, still more advantageously between 7 and 15 µm.
- For the purposes of the present invention, the term "lamellar mineral filler" is intended to mean any mineral filler or any synthetic filler of which the structure consists of a stack of elementary leaves. Advantageously the lamellar mineral filler according to the invention is a colorless or white lamellar mineral filler, mineral or synthetic particles of any shape, more advantageously selected in the group consisting of clay, talc, boron nitride, mica and mixtures thereof, more advantageously in the group consisting of mica, talc and mixtures thereof, still more advantageously it is talc, in particular HAR® talc such as the reference Talc Luzenac Har® T84 sold by Imerys. This talc has in particular the following properties:
- DL50 (µm) (mean particle size diameter by laser) = 10.5
- DS50 (µm) (mean particle size diameter by sedigraph) = 2
- Lamellarity index: (DL50 - DS50) / DS50 = (10.5-2) / 2 = 4.25.
- Whiteness (Minolta CR400, illuminant D65/2))Y L* (CIE) = 91
- Typical aspect ratio (length/thickness) = 120
- The lamellar mineral filler according to the invention can be obtained by the process as described in
US6348536 . - The lamellar mineral filler is preferably used in pencil lead in order to have an impact on the vividness of the laydown on the paper and/or on the smoothness or softness of the writing/drawing/coloring experience.
- In an advantageous embodiment the total lamellar mineral filler content of the pencil lead according to the invention is in the range 5 - 40%, advantageously 10 - 25 %, more advantageously 10 - 15 %, by weight relative to the total weight of the lead.
- A further object of the invention is the use of a lamellar mineral filler having a lamellarity index greater than 2.8 as defined previously to improve the flexural resistance and/or the smoothness, and/or the vividness of a polymer-based extrudable non-calcined pencil lead, in particular when writing/drawing/coloring on paper.
- The pencil lead according to the invention can also contain a slip agent. Indeed slip agents are able to modify the surface properties of a film and thus lower the friction between film layers and other surfaces. To be particularly effective the slip agent needs to migrate out of the polymer to the surface and therefore it is advantageous for it to have a degree of incompatibility with the polymer.
- The benefits of the use of a slip agent in the pencil lead composition are: enhance both appearance and function (to improve smoothness and glides), improve the flow characteristic of the polymer during processing. Slip agents are effective because of their natural tendency "to bloom" to the surface of the film after extrusion. The slip agent to be used in the pencil lead according to the present invention is advantageously selected in the group consisting of amides such as ethylene bis stearamide, oleamide, erucamide and stearamide, glycerol derivatives such as glycerol esters such as glycerol ethylhexyl polyhydroxystearate, glycerol behenate, glycerol dibehenate, tribehin, glycerol trihydroxystearate and mixtures thereof, esters of stearic acid, in particular tetraester of stearic acid, esters of pentaerythritol such as pentaerythrityl tetrastearate, and mixtures thereof. More advantageously the slip agent is a glycerol ester, preferably selected in the group consisting of glycerol ethylhexyl polyhydroxystearate, glycerol dibehenate and mixtures thereof. Advantageously, the total slip agent content of the pencil lead according to the present invention is in the range 0.5 - 5%, more advantageously 2 - 4 %, by weight relative to the total weight of the lead.
- The pencil lead according to the present invention can advantageously contain at least a coloring agent.
- Advantageously the coloring agent is selected in the group consisting of dyes, pigments and mixtures thereof, more advantageously in the group consisting of organic or inorganic pigments, dyes or lacquered dyes, coated mica as well as coated or uncoated metal bronzed, TiO2, carbon black, graphite and mixture of these coloring agents. The term "pigments" should be understood as meaning white or coloured, mineral or organic particles of any form, which are insoluble in the medium, and which are intended to color the lead. The term "dyes" should be understood as meaning white or colored, mineral or organic particles of any form, which are soluble in the medium, and which are intended to color the lead. In an advantageous embodiment, the coloring agent is selected in the group consisting of pigments and mixtures thereof, still more advantageously in the group consisting of organic pigments, TiO2 and mixtures thereof. Depending on the desired color of the lead, the pigment is a red, black, yellow, orange, blue, magenta or violet pigment, and mixtures thereof. The pigment and/or carbon black can be coated or mixed with a polyolefin wax (for example in the form of a masterbatch, a pigmentary preparation or a dispersion of pigment in a polyolefin wax) as mentioned in
WO2016/097555 andWO2016/097533 . The coloring agent gives the lead color. - Advantageously, the total coloring agent content of the pencil lead according to the invention is in the range 2 - 25%, more advantageously 10 - 20 %, by weight relative to the total weight of the lead.
- According to this embodiment, preferably said pencil is a color pencil lead or a graphite pencil lead, advantageously a color pencil lead.
- Advantageously, according to this embodiment wherein the pencil lead according to the present invention contains at least coloring agent (colored pencil lead), the obtained deposit (laydown) when applied on a surface, such as paper, exhibits a good intensity (or vividness) of the color. According to a preferred embodiment of the invention, the pencil flexural resistance is higher than 0.70 daN.
- The pencil lead according to the present invention can contain a wax.
- For the purposes of the present invention, the term "wax" is intended to mean a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, and having a melting point of 30°C or more, which may be up to 180°C
- In the present invention, the melting point corresponds to the transition stage between a fully crystalline or partially crystalline solid state and an amorphous liquid of variable viscosity, as described in ISO 11357-3; 2011. The term "transition", also referred to as "fusion", is characterized by an endothermic peak in the DSC curve.
- The melting point of wax can be measured by differential scanning calorimetry (DSC) using a TA Instruments Q20 apparatus, on a temperature range from 20 to 90°C, at cooling/ heating speeds of 10°C/minute.
- This measurement is made with 5 mg of sample mass.
-
- 1. Equilibrate at 0°C
- 2. Mark end of cycle
- 3. Ramp: 10°C/min to 90°C
- 4. Isothermal for 2 min
- 5. Ramp: 10°C/min to 0°C
- 6. Isothermal for 2 minutes
- 7. End of method
- The waxes may be hydrocarbon-based waxes, lignite-waxes, amide waxes, fatty acids, fatty acid esters, and/or ester waxes, and mixtures thereof, and may be of plant, mineral, animal and/or synthetic origin.
- In particular, the waxes have a melting point of greater than 30°C and better still greater than 50°C, which may be up to 180°C.
- Advantageously the wax according to the invention is selected in the group consisting of ester waxes, chosen among stearates waxes (melting point: 120-160°C) such as calcium stearate, lignite waxes such as montan waxes, amide waxes, hydrocarbon-based waxes such as paraffin (melting point: 50-60°C), fatty acids such as stearic acid and palmitic acid, fatty acid esters and mixtures thereof, preferably ester waxes, more preferably stearate waxes, more advantageously it is calcium stearate. It is indeed particularly advantageous if the wax is formed of calcium stearate or comprises calcium stearate.
- Advantageously the total wax content of the pencil lead according to the invention is in the range 10 - 40%, advantageously 20 - 35 %, by weight relative to the total weight of the lead.
- The pencil lead according to the present invention can contain additional filler, different from the described lamellar mineral filler having a high lamellarity index, such as mineral fillers, for example chosen from phyllosilicates, chalk, barite, kaolin, bentonite and mixtures thereof. Advantageously it does not contain any other filler than the lamellar mineral filler having a lamellarity index greater than 2.8 according to the invention.
- The pencil lead according to the present invention can contain an additive. This additive can be selected from additives which are well known to the person skilled in the art in the field of pencil leads, advantageously it is selected in the group consisting of lubricants such as zinc stearate, plasticizers such as phthalate, adipate, benzoate, sebacate and/or citrate plasticizers, in particular dibenzoate, surface-active agents, thermal stabilizers and mixtures thereof.
- Advantageously the total additive content of the pencil lead according to the invention is in the range 3 - 10%, advantageously 5 - 9 %, by weight relative to the total weight of the lead.
- The pencil lead according to the invention can be a color pencil lead or a graphite pencil lead, advantageously it is a color pencil lead.
- In the case where the pencil lead is a graphite pencil lead, the coloring agent comprises graphite, carbon black or mixture thereof.
- In a particular embodiment of the present invention, the pencil lead has a diameter between 2 and 3.9 mm; advantageously it is a lead having a diameter between 2 and 2.3 mm (thin lead) or a lead having a diameter between 3 and 3.8 mm (thick lead) or a lead having a diameter between 3.4 and 3.8 mm (very thick lead).
- Advantageously, the lead according to the present invention can have a hexagonal, round or triangular cross section, advantageously a round or hexagonal cross section.
- The lead according to the present invention can be manufactured via processes that are well known to those skilled in the art.
- For example, all the components are mixed together and the mixture obtained is extruded at suitable temperatures. The lead obtained is then cooled. It is thus not calcined and/or baked.
- The lead according to the present invention thus has sufficient color vividness while at the same time having good mechanical properties, in particular in terms of flexural strength and/or impact strength, and while producing a continuous deposit on paper with smoothness. The flexural strength should be understood as the strength and the shock resistance of the pencil. The impact strength can be measured by Charpy impact test according to the standard NF EN ISO 179-1 of 2010.
- According to the invention, it is possible to provide a lead for writing and/or coloring, whose tensile strength and flexural strength have been improved and which also improved elasticity.
- The invention also relates to a pencil comprising a lead according to the present invention, in particular a pencil coated with wood or with synthetic wood material, comprising optionally an intermediate protective layer, for example, as described in patent applications
,WO 01/43987 WO 2016/097554 andWO 2017/220914 . - The pencil according to the invention can be a color pencil or a graphite pencil, advantageously it is a color pencil.
- Advantageously, the pencil according to the invention is obtained by coextrusion of the lead and of the synthetic wood material and optionally of the intermediate protective layer.
- In particular, the synthetic wood material is based on styrene polymer, and the intermediate protective layer can also plays the role of adhesion layer if the lead comprises a polyolefin polymer and advantageously the intermediate protective layer can comprise a mixture of EVA and of polystyrene as described in
WO 2016/097554 or an ethylene (C1-C4 alkyl) acrylate copolymer, alone or as a blend with a styrene polymer as described inWO2017/220914 . - Advantageously, the synthetic wood material is expanded so as to have a density equivalent to natural wood.
- In a particular embodiment of the present invention, the pencil according to the invention comprises an additional decorative layer, advantageously of varnish, surrounding the synthetic wood material, in particular concentrically. Advantageously, the decorative layer is made of a material that is compatible with that of the synthetic wood material. Advantageously, the pencil according to the present invention can have a hexagonal, round or triangular cross section, advantageously a round or hexagonal cross section.
- Advantageously, it can comprise a means for erasing, such as an eraser, at the unsharpened end of the pencil.
- The invention finally concerns the use of a lamellar mineral filler having a lamellarity index greater than 2.8 as defined above to improve the flexural resistance and/or the smoothness, and/or the vividness of a polymer-based extrudable non-calcined pencil lead.
- The invention will be understood better upon reading the description of the following examples which are given as a non-limiting indication.
- The expression "between ... and ..." or "ranging from ...to ..." should be understood as including the values of the limits.
- Examples of compositions of pencil lead according to the present invention (examples 1, 2, 3 and 4) containing a mineral lamellar filler having a lamellarity index of 4.25 (Talc Luzenac Har® T84) were compared with comparative compositions of pencil lead (comparative examples 1 and 2) wherein the high lamellarity mineral filler has been replaced by a mineral filler with a lamellarity index of lower than 2.8 (Luzenac 20MO talc having the following properties: DL50 (µm) (particle size by laser) = 10.5; DS50 (µm) (particle size by sedigraph) = 5; Lamellarity index : (DL50 - DS50) / DS50 = (10.5-5) / 5 = 1.1).
- The pencil leads are produced by carrying out the steps detailed below:
- Mixing and granulating all formulation components of the lead to form a writing substance granulate;
- Extruding the writing substance granulate at a temperature in the range of 130 to 200°C on an extruder by a suitable mouthpiece to form endless writing substance strands;
- Cooling and hardening the endless writing substance strand; and
- Cutting the endless writing substance strand to final lengths, in particular to the required pencil length.
- The properties of color vividness (ΔC) and Pencil Flexural resistance (Flexion (daN)) of the leads were measured as follow:
- The pencil flexural resistance test was carried out in order to check the strength and the shock resistance of the pencil.
- The characteristics of the test were as follows:
- Equipment: Dynamometer LLOYD-AMETEK Instrument type, U-bracket span of 6 cm, Sensor ADAMEL DY20 Chatillon Instrument type TCD110 50 daN
- Descent speed of sensor: 50 mm.min-1
-
- 1. Turn on the dynamometer.
- 2. Locate the sensor in the up position.
- 3. Fix the pencil on the U-bracket.
- 4. Go down the needle.
- 5. Record the results expressed in daN.
- The test protocol is as follows:
- - Writing apparatus HUTT HST 10 or equivalent used under the following conditions:
- Writing speed: 4.5 m/min
- Writing angle: 70°
- Other parameters: refer to table below
-
- 1) Prepare the writing article in the appropriate supports, sharpen the lead if necessary.
- 2) Produce the rubbings according to the parameters indicated in the preceding table
- 3) Measure the density of the color of the rubbing with the help of the spectroEye (minimum 2 measurements per blackness) according to DIN 16536 NB
-
- To determine the "vividness" of a lead in accordance with the invention, the measurement of colorimetry can be measured. The "vividness" should be understood as the intensity of the deposit i.e. laydown of the pencil when applied on a surface. The vividness can be measured by colorimetry test by measuring the color difference ΔC between a sample color and a comparative color.
- The density of the color of the deposit has been measured in the CIE L*a*b* system using a KONICA MINOLTA CM-3610 A model spectrocolorimeter in the CIE L a b system (illuminant: D65, angle 10°, specular components included).
- According to this system, L* indicates the lightness of the color of the deposit. The lowest is the value of L, the most intense (or "darker") is the color of the deposit. The chromaticity coordinates are expressed by the parameters a* and b*, a* indicating the axis of red/green shades and b* the axis of yellow/blue shades. The chromaticity C* is obtained from the following formula.
- All colorimetric measurements have been done on a deposit made on a white paper. The greater the value of C* (also called C*ab), the better the saturation of the color of the deposit.
- The composition (in weight %) and results are indicated in tables 2 and 3 below:
Table 2: polymer = GPPS Trade name Example 1 Example 2 Example 3 Comparative example 1 Polymer GPPS 36% 33% 33% 36% Lamellar mineral filler Talc Luzenac Har® T84 14% 14% 14% 0% Mineral filler Talc 20 Mo 0% 0% 0% 14% Wax Calcium stearate 26% 26% 26% 26% Coloring agent Organic pigment 7.75% 7.75% 7.75% 7.75% Coloring agent TiO2 7.75% 7.75% 7.75% 7.75% Additive Plasticizer Dibenzoate 6% 6% 6% 6% Additive Lubricant Zinc stearate 2.5% 2.5% 2.5% 2.5% Slip agent Glycerol ethylhexyl polyhydroxystearate 0% 3% 0% 0% Slip agent Glycerol dibehenate 0% 0% 3% 0% Total 100% 100% 100% 100% Flexion (daN) 0.852 0.889 0.765 0.755 C* 18.98 20.35 19.53 17.15 Table 3: polymer = ABS Trade name Example 4 Comparative example 2 Bonding agent ABS 36% 36% Mineral filler Talc 20MO 0% 14% Lamellar mineral filler Talc Luzenac Har® T84 14% 0% Wax Calcium stearate 26% 26% Coloring agent Organic pigment 7.75% 7.75% TiO2 7.75% 7.75% Additive Plasticizer Dibenzoate 6% 6% Additive Lubricant Zinc stearate 2.5% 2.5% Slip agent Glycerol ethylhexyl polyhydroxystearate 0% 0% Total 100% 100% Flexion (daN) 0.940 0.920 C* 19.59 18.75 - As a consequence, the leads of examples 1, 2, 3 and 4 according to the invention which comprise a high lamellarity mineral filler have enhanced flexural properties and color vividness compared to the leads of comparative examples 1 and 2 wherein said high lamellarity mineral filler has been replaced by a low lamellarity mineral filler.
- In addition, the smoothness, the glide as well as the softness of the lead has been evaluated by writing, drawing and/or coloring manually with the leads according to examples 1 to 4 and it has been observed that they deliver an effortless and smooth-gliding writing, drawing and/or coloring experience on paper.
- Apparatus KONICA MINOLTA model CM-3610 A
- Pencil sharpener
- Viewing angle of light: 10°
| Parameters for producing the rubbings | |
| Article type | Lead |
| Diameter lead (mm) | 2.14 |
| Paper feed (mm/min) | 0.15 |
| Total weight article / support / additional weight (g) | 175 |
| Writing length for axial rotation of the article (m) | 9 |
| Writing length (m) | 40 |
| Paper type | AURORA ISO-14145 |
Claims (18)
- A polymer-based extrudable non-calcined pencil lead comprising a lamellar mineral filler having a lamellarity index greater than 2.8, advantageously greater than 3.5, in particular greater than 4.
- The pencil lead according to claim 1, characterized in that the lamellar mineral filler is talc.
- The pencil lead according to any of claim 1 or 2, characterized in that the total lamellar mineral filler content is in the range 5 - 40%, advantageously 10 - 25 %, more advantageously 10 - 15 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 3, characterized in that the polymer is selected from the group consisting of homo or copolymers of polyesters; homo or copolymers of polyolefins such as polyethylene, polypropylene and mixtures thereof; homo or copolymers of styrene polymers, such as polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers, general purpose polystyrene, high impact polystyrene and mixtures thereof.
- The pencil lead according to claim 4, characterized in that the polymer is selected from the group consisting of homo or copolymers of styrene polymers, advantageously in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers, styrene-butadiene copolymers and mixtures thereof, still more advantageously in the group consisting of general purpose polystyrene, acrylonitrile-butadiene-styrene copolymers and mixtures thereof, in particular it is general purpose polystyrene.
- The pencil lead according to any one of claims 1 to 5, characterized in that the total polymer content is in the range 20 - 45%, advantageously 25 - 40 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 6, characterized in that it contains a slip agent, advantageously selected in the group consisting of amides such as ethylene bis stearamide, oleamide, erucamide and stearamide, glycerol derivatives such as glycerol esters such as glycerol ethylhexyl polyhydroxystearate, glycerol behenate, glycerol dibehenate, tribehin, glycerol trihydroxystearate and mixtures thereof, esters of stearic acid, in particular tetraester of stearic acid, esters of pentaerythritol such as pentaerythrityl tetrastearate, and mixtures thereof, advantageously glycerol esters, preferably selected in the group consisting of glycerol ethylhexyl polyhydroxystearate, glycerol dibehenate and mixtures thereof.
- The pencil lead according to claim 7, characterized in that the total slip agent content is in the range 0.5 - 5%, advantageously 2 - 4 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 8, characterized in that it contains a coloring agent, advantageously selected in the group consisting of dyes, pigments and mixtures thereof, more advantageously in the group consisting of pigments and mixtures thereof, still more advantageously in the group consisting of organic pigments, TiO2 and mixtures thereof.
- The pencil lead according to claim 9, characterized in that the total coloring agent content is in the range 2 - 25%, advantageously 10 - 20 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 10, characterized in that it contains a wax, advantageously selected in the group consisting of ester waxes chosen among stearate waxes such as calcium stearate, lignite waxes such as montan waxes, amide waxes, hydrocarbon-based waxes such as paraffin, fatty acids such as stearic acid and palmitic acid, fatty acid esters and mixtures thereof, preferably ester waxes, more preferably stearate waxes, more advantageously it is calcium stearate.
- The pencil lead according to claim 11, characterized in that the total wax content is in the range 10 - 40%, advantageously 20 - 35 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 12, characterized in that it contains an additive, advantageously selected in the group consisting of lubricants, plasticizers, surface-active agents, thermal stabilizers and mixtures thereof.
- The pencil lead according to claim 13, characterized in that the total additive content is in the range 3 - 10%, advantageously 5 - 9 %, by weight relative to the total weight of the lead.
- The pencil lead according to any one of claims 1 to 14, characterized in that it is a color pencil lead or a graphite pencil lead, advantageously a color pencil lead.
- The pencil lead according to any one of claims 1 to 15, characterized in that it is extruded.
- A pencil comprising a lead as claimed in any one of claims 1 to 16, advantageously it is a color pencil.
- Use of a lamellar mineral filler having a lamellarity index greater than 2.8 as defined in any of claims 1 to 16 to improve the flexural resistance and/or the smoothness, and/or the vividness of a polymer-based extrudable non-calcined pencil lead.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20305003.4A EP3845616B1 (en) | 2020-01-06 | 2020-01-06 | Lead for pencil for writing, drawing, marking, plotting and/or coloring |
| MX2020012470A MX2020012470A (en) | 2020-01-06 | 2020-11-19 | PENCIL LEAD TO WRITE, DRAW, MARK, TRACE AND/OR COLOUR. |
| BR102020023663-6A BR102020023663A2 (en) | 2020-01-06 | 2020-11-19 | PENCIL TIP FOR WRITING, DRAWING, MARKING, PLOTTING AND/OR COLORING |
| US17/130,322 US20210206989A1 (en) | 2020-01-06 | 2020-12-22 | Lead for pencil for writing, drawing, marking, plotting and/or coloring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20305003.4A EP3845616B1 (en) | 2020-01-06 | 2020-01-06 | Lead for pencil for writing, drawing, marking, plotting and/or coloring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3845616A1 true EP3845616A1 (en) | 2021-07-07 |
| EP3845616B1 EP3845616B1 (en) | 2025-12-03 |
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ID=69185546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20305003.4A Active EP3845616B1 (en) | 2020-01-06 | 2020-01-06 | Lead for pencil for writing, drawing, marking, plotting and/or coloring |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20210206989A1 (en) |
| EP (1) | EP3845616B1 (en) |
| BR (1) | BR102020023663A2 (en) |
| MX (1) | MX2020012470A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001043987A1 (en) | 1999-12-13 | 2001-06-21 | Conte | Method for making a writing or colouring pencil by triple extrusion and writing or colouring pencil comprising an intermediate protective layer |
| US6348536B1 (en) | 1997-04-04 | 2002-02-19 | Talc De Luzenac | Lamellar filler process for the treatment of polymers |
| US6815471B2 (en) * | 1998-06-26 | 2004-11-09 | Binney & Smith Inc. | Erasable colored pencil lead |
| WO2016097533A1 (en) | 2014-12-16 | 2016-06-23 | Orange | Method for controlling a phone call initiated by a terminal connected to a communications network |
| WO2016097555A1 (en) | 2014-12-17 | 2016-06-23 | Conte | Colour pencil lead |
| WO2016097554A1 (en) | 2014-12-17 | 2016-06-23 | Conte | Pencil for writing or colouring |
| WO2017220914A1 (en) | 2016-06-21 | 2017-12-28 | Conte | Writing or coloring pencil |
| US20180071181A1 (en) * | 2015-03-18 | 2018-03-15 | Imerys Talc Europe | Cosmetic compositions comprising a talc particulate |
| WO2018189467A1 (en) * | 2017-04-10 | 2018-10-18 | Societe Bic | Lead for paper pencil |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283648A (en) * | 1995-04-10 | 1996-10-29 | Pilot Precision Co Ltd | Pencil lead |
| DE102008034014B4 (en) * | 2008-07-15 | 2011-06-16 | J. S. Staedtler Gmbh & Co. Kg | Mine for writing, drawing and / or painting equipment |
| DE202008009751U1 (en) * | 2008-07-15 | 2009-08-27 | J. S. Staedtler Gmbh & Co. Kg | Writing, drawing, painting or cosmetic pencil |
| EP2770029B1 (en) * | 2013-02-22 | 2019-06-12 | Imertech Sas | Talc composition and uses thereof |
| FR3030364B1 (en) * | 2014-12-17 | 2017-01-13 | Conte | PENCIL MINE WITH PAPER |
| CN107043577B (en) * | 2017-04-20 | 2021-02-02 | 浙江华科笔业有限公司 | Full-plastic color pen and preparation method thereof |
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2020
- 2020-01-06 EP EP20305003.4A patent/EP3845616B1/en active Active
- 2020-11-19 MX MX2020012470A patent/MX2020012470A/en unknown
- 2020-11-19 BR BR102020023663-6A patent/BR102020023663A2/en active IP Right Grant
- 2020-12-22 US US17/130,322 patent/US20210206989A1/en not_active Abandoned
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6348536B1 (en) | 1997-04-04 | 2002-02-19 | Talc De Luzenac | Lamellar filler process for the treatment of polymers |
| US6815471B2 (en) * | 1998-06-26 | 2004-11-09 | Binney & Smith Inc. | Erasable colored pencil lead |
| WO2001043987A1 (en) | 1999-12-13 | 2001-06-21 | Conte | Method for making a writing or colouring pencil by triple extrusion and writing or colouring pencil comprising an intermediate protective layer |
| WO2016097533A1 (en) | 2014-12-16 | 2016-06-23 | Orange | Method for controlling a phone call initiated by a terminal connected to a communications network |
| WO2016097555A1 (en) | 2014-12-17 | 2016-06-23 | Conte | Colour pencil lead |
| WO2016097554A1 (en) | 2014-12-17 | 2016-06-23 | Conte | Pencil for writing or colouring |
| US20170349775A1 (en) * | 2014-12-17 | 2017-12-07 | Conte | Colour pencil lead |
| US20180071181A1 (en) * | 2015-03-18 | 2018-03-15 | Imerys Talc Europe | Cosmetic compositions comprising a talc particulate |
| WO2017220914A1 (en) | 2016-06-21 | 2017-12-28 | Conte | Writing or coloring pencil |
| WO2018189467A1 (en) * | 2017-04-10 | 2018-10-18 | Societe Bic | Lead for paper pencil |
Non-Patent Citations (1)
| Title |
|---|
| G.BAUDETJ. P. RONA, IND. MIN. MINES ET CARR. LES TECHN., June 1990 (1990-06-01), pages 55 - 61 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3845616B1 (en) | 2025-12-03 |
| BR102020023663A2 (en) | 2021-07-13 |
| US20210206989A1 (en) | 2021-07-08 |
| MX2020012470A (en) | 2021-07-07 |
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